Novel colorimetric membranes based on polylactic acid-grafted-citrated methacrylated urethane (PLA-CMU) to monitor cod freshness

Halochromic agent is easy to fall off from the surface of colorimetric membranes during fish freshness monitoring, which would decay the test accuracy. In order to increase its anchoring, citrated methacrylated urethane (CMU) synthesized by using tributyl citrate, β-hydroxyethyl methacrylate and diphenyl-methane-diisocyanate as a halochromic agent was grafted on polylactic acid (PLA). The CMU grafted PLA (PLA-CMU) together with tetrabutylammonium chloride (TBAC) prepared colorimetric membranes via electrospinning. 1H NMR and FTIR analysis showed successful bonding between CMU and PLA, and PLA-CMU grafting efficiency reached to the maximum value of 11.15%. Moreover, DSC confirmed that PLA-CMU existed low cold-crystallization temperature due to the excellent compatibility of CMU with PLA, which enhanced the anchoring of CMU effectively. Nanofiber-based PLA-CMU/TBAC colorimetric membrane enhanced the probability of molecules being captured due to its porous structure and large specific surface area. In addition, the increase in hydrophilicity of the membrane can provide a microenvironment for liquid phase reaction, exhibiting obvious color-changing sensitivity during cod freshness monitoring, from white color to light orange or pink with the deterioration of cod at 25 °C and 4 °C respectively. The results demonstrate PLA-CMU/TBAC colorimetric membranes would provide a simple and promising strategy for monitoring fish freshness.